CN1424304A - Preparation for aniline, phenol and derivative thereof - Google Patents
Preparation for aniline, phenol and derivative thereof Download PDFInfo
- Publication number
- CN1424304A CN1424304A CN 02147864 CN02147864A CN1424304A CN 1424304 A CN1424304 A CN 1424304A CN 02147864 CN02147864 CN 02147864 CN 02147864 A CN02147864 A CN 02147864A CN 1424304 A CN1424304 A CN 1424304A
- Authority
- CN
- China
- Prior art keywords
- preparation
- aniline
- metal
- derivative
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 316
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims description 134
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 244
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims abstract description 223
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 163
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 162
- 238000006243 chemical reaction Methods 0.000 claims abstract description 143
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001868 water Inorganic materials 0.000 claims abstract description 38
- 125000001424 substituent group Chemical group 0.000 claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 128
- 238000000034 method Methods 0.000 claims description 92
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 84
- 150000001875 compounds Chemical class 0.000 claims description 63
- 229910001509 metal bromide Inorganic materials 0.000 claims description 55
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 50
- 230000008569 process Effects 0.000 claims description 47
- 239000000376 reactant Substances 0.000 claims description 47
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 45
- 150000004692 metal hydroxides Chemical class 0.000 claims description 45
- 229910021529 ammonia Inorganic materials 0.000 claims description 41
- 239000012752 auxiliary agent Substances 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 33
- 230000003647 oxidation Effects 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 230000008929 regeneration Effects 0.000 claims description 25
- 238000011069 regeneration method Methods 0.000 claims description 25
- 150000001412 amines Chemical class 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 21
- 230000000694 effects Effects 0.000 claims description 21
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- -1 vitriol Chemical compound 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052693 Europium Inorganic materials 0.000 claims description 18
- 229910052779 Neodymium Inorganic materials 0.000 claims description 18
- 229910052772 Samarium Inorganic materials 0.000 claims description 18
- 229910052771 Terbium Inorganic materials 0.000 claims description 18
- 229910052775 Thulium Inorganic materials 0.000 claims description 18
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 18
- 229910052787 antimony Inorganic materials 0.000 claims description 18
- 229910052793 cadmium Inorganic materials 0.000 claims description 18
- 229910052792 caesium Inorganic materials 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 229910052733 gallium Inorganic materials 0.000 claims description 18
- 229910052732 germanium Inorganic materials 0.000 claims description 18
- 229910052738 indium Inorganic materials 0.000 claims description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims description 18
- 229910052745 lead Inorganic materials 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 18
- 229910052700 potassium Inorganic materials 0.000 claims description 18
- 229910052701 rubidium Inorganic materials 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 229910052712 strontium Inorganic materials 0.000 claims description 18
- 229910052716 thallium Inorganic materials 0.000 claims description 18
- 229910052718 tin Inorganic materials 0.000 claims description 18
- 229910052727 yttrium Inorganic materials 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 150000004768 bromobenzenes Chemical class 0.000 claims description 15
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 14
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 150000002989 phenols Chemical class 0.000 claims description 14
- 229910052720 vanadium Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 12
- 229910000765 intermetallic Inorganic materials 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 12
- 150000003016 phosphoric acids Chemical class 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 11
- 229910052735 hafnium Inorganic materials 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 11
- 229910052702 rhenium Inorganic materials 0.000 claims description 11
- 150000003335 secondary amines Chemical class 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 10
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 238000001149 thermolysis Methods 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052706 scandium Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 238000005893 bromination reaction Methods 0.000 claims description 6
- QARVLSVVCXYDNA-IDEBNGHGSA-N bromobenzene Chemical group Br[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 QARVLSVVCXYDNA-IDEBNGHGSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000011964 heteropoly acid Substances 0.000 claims description 6
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 6
- 229910001510 metal chloride Inorganic materials 0.000 claims description 6
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 6
- 229910001511 metal iodide Inorganic materials 0.000 claims description 6
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 6
- 229910052755 nonmetal Inorganic materials 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 238000005194 fractionation Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 230000000536 complexating effect Effects 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 4
- 239000002815 homogeneous catalyst Substances 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 230000009257 reactivity Effects 0.000 claims description 4
- 239000011833 salt mixture Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 230000000994 depressogenic effect Effects 0.000 claims description 2
- 238000003795 desorption Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 238000006213 oxygenation reaction Methods 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 241000894007 species Species 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims 10
- PVFOHMXILQEIHX-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-bromophenyl)ethyl]purin-6-amine Chemical compound C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Br PVFOHMXILQEIHX-UHFFFAOYSA-N 0.000 claims 3
- 230000001590 oxidative effect Effects 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 9
- 229910000435 bromine oxide Inorganic materials 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 230000009466 transformation Effects 0.000 description 19
- 229910001220 stainless steel Inorganic materials 0.000 description 13
- 239000010935 stainless steel Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 235000003140 Panax quinquefolius Nutrition 0.000 description 3
- 240000005373 Panax quinquefolius Species 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000001546 nitrifying effect Effects 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000272165 Charadriidae Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 244000257039 Duranta repens Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003286 Ni-Mn Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 210000003050 axon Anatomy 0.000 description 1
- KZSBGJNGPFPFOH-UHFFFAOYSA-N benzene;iron Chemical compound [Fe].C1=CC=CC=C1.C1=CC=CC=C1 KZSBGJNGPFPFOH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/02—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing phenylamine or phenol and its derivative includes such steps as the benzene or the benzen containing substituents reacting on bromine to obtain bromobenzen or the bromobenzene containing substituents, and reacting on the oxide and/or hydroxide of metal to obtain phenylamine or its derivative containing substituent or reacting on the oxide and/or hydroxide of metal and H2O to obtain phenol and its derivative containing substituents, as well as water as by-product. Its advantages are cyclic use of bromine and metal oxide, high conversion rate and high selectivity.
Description
Technical field:
The invention belongs to the preparation method of a kind of aniline, phenol derivmives blend biology.
Background technology:
(1) aniline is commonly called as Allihn Buddhist nun oil, is colourless oil liquid.Aniline is one of important Organic Chemicals.The U.S., West Europe and Japan are main country of consumption of world's aniline and area, account for 80% of world's aggregate consumption.In these countries and regions consumption structures, the consumption of MDI occupies first, accounts for about 80% of aggregate consumption.MDI is one of raw material of producing urethane.Aniline also can be used for preparing rubber ingredients (account for aniline consumption about 11%), dye well pigment dyestuff (accounting for 3%).Aniline also can be used for industrial circles such as agricultural chemicals, medicine and special fibre in addition.
Aniline Production technology has nitre benzene benzene iron powder reducing method, halogeno-benzene ammoniation process, phenol ammoniation process and oil of mirbane shortening method at present.Oil of mirbane iron powder reducing method is an industrial process the earliest, and is now superseded substantially; The halogeno-benzene ammoniation process is seldom selected this technology in practice.Aniline Production mainly adopts phenol ammoniation process and oil of mirbane shortening method at present.
Phenol ammoniation process advantage is that raw material is simple, the catalyzer cheapness, and good product quality, the three wastes are few, be suitable for large scale continuous prod and coproduction pentanoic as required, but cost are than hydrogenation of chloronitrobenzene method height.Have only U.S. Aristech company to utilize this method to produce aniline at present.
It is present each big producer method with the most use in the world that the hydrogenation of chloronitrobenzene reduction method prepares aniline.It is divided into two kinds of gas phase hydrogenation and liquid-phase hydrogenatins according to reaction characteristics.Liquid-phase hydrogenatin productive rate height, throughput is big, and side reaction is few, but the difficult solvent recovery of catalyzer, operation more complicated, and cost of equipment height.The gas phase hydrogenation method is divided into Fixed Bed Gas Phase hydrogenation technique and fluidized-bed gas phase hydrogenation technology again.Fixed Bed Gas Phase shortening technology maturation, equipment and simple to operate, maintenance cost is low, the quality product height.Shortcoming is easily local superheating to take place and cause side reaction and catalyst deactivation, must the periodic replacement catalyzer.Fluidized bed gas-phase catalytic hydrogenation has better been controlled temperature of reaction, avoids local superheating, reduces side reaction.This technology shortcoming is to operate complexity, and catalyst abrasion is big, and structure of reactor is complicated and need separating catalyst, causes operation standing charges height.
Du pont company proposed from benzene and NH on its United States Patent (USP) in 1977
3Straight by synthetic aniline, this method has much competitive power.This technology is used Ni/NiO/ZrO
2Do " Cataloreactant ", it is reduced in reaction process, is regenerated but can reoxidize.The aniline productive rate of this method is 12%, but needs the high like this pressure of 7000psi, and this has hindered its commercial promise.
Mitsui Toatsu researchist has reported and has used NH
3And H
2O is converted into phenol and aniline (Japan KokaiJ02115138-A (1990)) with benzene.But the aniline productive rate has only 1.9%.
Durante etc. have proposed aniline (US Patent NO 5,861,536) is directly synthesized in the ammonification of benzene catalyzed oxidation.Molecular oxygen is as oxygenant, and catalyzer then is made up of carrier, transition metal and monokaryon or double-core part.Also have other to come direct method (as: 1) Canadian Patent WO 553, the 988 to Thomas that synthesize aniline by benzene etc. with molecular oxygen; 2) J Becker etc., Catal.Lett.54 (1998) 124-128; 3) PCT application WO 99/10,311to Axon et al; 4) PCT application WO 00/09,473 to Stilt et al) but these methods by the directly synthetic aniline of benzene all do not have commercialization, because the transformation efficiency of benzene selectivity low and aniline is low.
Alfred Hagemeyer etc. has reported with solid-state Cataloreactants and has made oxygenant, by the directly synthetic aniline (Applied Catalysis A:General 227 (2002) 43-61) of benzene.Adopting its best Cataloreactant is Rh/Ni-Mn/K-TiO
2Can obtain 10% benzene transformation efficiency and＞95% aniline selectivity.Temperature of reaction is 300 ℃, and reaction pressure is 300bar, and this result of study is regarded as having commercial promise.But the benzene transformation efficiency is also too low.
(2) phenol is a kind of important chemical material.At present both at home and abroad mainly in order to benzene be raw material sulfonation method, draw a western Hooke method, chlorobenzene hydrolysis method, hexanaphthene method and cumene method synthesizing phenol.These multistep synthesis methods exist reactions steps many, complex technical process, problem such as the low and equipment corrosion of total recovery is serious.Since the sixties, various countries are devoted to the development research of benzene single stage method synthesizing phenol, and obtain certain effect.The method that is proposed has with N
2O is an oxygenant, and Fe-ZSM-5 is the gas-solid-liquid phase method of catalyzer; Ti-Si-Pd is a catalyzer, O
2-H
2Solution-air phase method for oxygenant; O
2-H
2The electrochemical synthesis method of fuel cell reaction; The Fe-Cu-O/ sepiolite is a catalyzer, and hydrogen peroxide is gas one solid phase method and the PdCl of hydroxylating agent
2-CuCl
2/ sepiolite catalysis benzene is liquid one solid phase method of phenol.
Above method obtains some effects from different aspects, but has different problems, and it is low to produce effects as phenol, the catalyzer costliness, and the temperature of reaction height, used oxygenant is (as N
2O) source is difficult for, and inconvenience is used.Therefore, lack Practical significance.
Summary of the invention:
The purpose of this invention is to provide preparation method, the especially aniline of a kind of aniline, phenol derivmives blend biology and the preparation method of derivative thereof, the preparation method of the preparation method of phenol derivmives blend biology and coproduction aniline and phenol derivmives blend biology.
The object of the present invention is achieved like this, and the preparation method of described aniline, phenol derivmives blend biology has adopted the synthetic new technological process of brand-new synthetic aniline, phenol derivmives blend biology and a coproduction aniline and phenol derivmives blend biology.This flow process comprises following step:
1) by benzene and contain various substituent benzene and bromine reaction generates bromobenzene or contains various substituent bromobenzene.This reaction is finished under metal and nonmetallic compound catalyst action, and HBr is a by product in reaction.By product HBr under catalyst action with oxygen or air in oxygen reaction, oxidation generates water and bromine, thereby reclaims the bromine among the HBr.
2) the 1st) in the step, the bromobenzene of generation or contain substituent bromobenzene derivative with metal oxide and/or metal hydroxides and ammonia or ammoniacal liquor and react and then generate the metal bromide that aniline and metal bromide or ammino close.
As the 1st) bromobenzene that makes of step and derivative thereof react with metal oxide and water and then generate corresponding phenol or phenol derivatives and metal bromide.
As the 1st) bromobenzene that makes and derivative thereof and ammoniacal liquor or volatile salt or ammonium bicarbonate aqueous solution and metal oxide be or/and the metal hydroxides reaction generates the mixture of aniline or anils and phenol or phenol derivatives, generated the metal bromide that metal bromide and ammino close in the reaction.
3) the 2nd) metal bromide that closes of the ammino that generates in the step resolves into metal bromide and ammonia under heating condition, to reclaim ammonia.Here the metal bromide of Sheng Chenging and the 2nd) metal bromide that generates in the step in oxygen or in the air high-temp combustion generate metal oxide and bromine, to reclaim bromine and metal oxide.
The net result of whole flow process is that by product is a water with benzene or benzene derivative, ammonia, oxygen (or in the air oxygen) synthetic aniline or anils.As synthetic phenols, then be with benzene or benzene derivative, water, oxygen (or in the air oxygen) synthesizing phenol or phenol derivatives.Bromine and metal oxide recycle in synthetic aniline and phenol and their derivative process, do not consume, and also do not have environmental pollution.
In above-mentioned flow process, if be example with benzene, the 1st) step reaction one way benzene transformation efficiency is more than 30%, generates the bromobenzene selectivity more than 97%, and the bromine per pass conversion reaches 100%.The 2nd) in the step, the bromobenzene transformation efficiency is more than 95%, and its aniline selectivity is more than 95%, and by product is to utilize in benzene (can get back to the 1st) step again).Reclaim in the reaction Br at HBr and metal bromide
2The rate of recovery more than 99%.
The above-mentioned total benzene and the substituent and the bromine of benzene react generation bromobenzene and the derivative of bromobenzene and the bromination reaction of HBr under the effect of catalyzer, wherein hydrogen bromide HBr can reclaim bromine through oxidation; Above-mentioned catalyzed reaction can be a heterogeneous catalytic reaction, also can be homogeneous catalytic reaction.And the reaction of said benzene or benzene derivative and bromine can be the reaction of operate continuously also can be still formula batch reactions, and said reaction can be benzene or benzene derivative and bromine charging simultaneously, after also can being an elder generation one, or a reactant once adds, another reactant adds in batches or continuously, said reaction can be carried out between-40 ℃ to 550 ℃, service temperature is-20 ℃ to 450 ℃ preferably, best service temperature is-20 ℃ to 300 ℃, said reaction pressure is between 0.1 normal atmosphere to 300 normal atmosphere, pressure range is between 0.5 normal atmosphere to 200 normal atmosphere preferably, preferably between 0.8 normal atmosphere to 50 normal atmosphere.The substituent of described benzene is selected from chloro thing, fluoro thing, bromo-derivative phenyl substituent, alkyl substituent, alkenyl substituted thing, alkynyl substituted thing, nitro substituent, sulfo group substituent, phenylol substituent, thiophenol base substituent, the anilino substituent that comprises benzene.Described catalyzer is metal oxide, metal chloride, metal fluoride, metal iodide, metal sulfate, metal phosphate, metal heteropolyacid salt, BF
3, the metal except that iron powder, and the arbitrary proportion mixture of above-listed compound, and the catalyzer iron powder uses as catalyzer commonly used at present in bromination reaction, but does not have document openly to use as metal oxide, metal chloride, metal fluoride, metal iodide, metal sulfate, metal phosphate, metal heteropolyacid salt, BF at present
3, the metal except that iron powder, and above-mentioned these catalyzer of the arbitrary proportion mixture of above-claimed cpd.Said catalyzer can be homogeneous catalyst or heterogeneous catalyst.Described catalyzer can be loaded catalyst or unsupported catalyst.Said loaded catalyst contains a kind of mutually active and carrier of being made up of one or more metallic compounds of mixture.Said carrier is meant to have a kind of being selected from as SiO at least
2, B
2O
3, Al
2O
3, GeO
2, TiO
2, ZrO
2, Nb
2O
5, Ta
2O
5, activated carbon etc. metallic compound or nonmetal or nonmetallic compound.Said activity of such catalysts is Li mutually, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Gr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, the oxide compound of Gd, fluorochemical, muriate, bromide, iodide, phosphoric acid salt, vitriol, carbonate, silicate, borate, and their mixture or their mixture and Ru, Rh, Pd, Ir, Pt, Ag, the mixture of metals such as Au and metallic compound.Bromination reaction of the present invention can adopt: metal oxide, metal chloride, metal fluoride, metal iodide, metal sulfate, metal phosphate, metal heteropolyacid salt, BF
3, the metal except that iron powder, and these catalyzer of the arbitrary proportion mixture of above-claimed cpd, can adopt present general bromination reaction condition and mode to carry out, its gained result is similar with employing iron powder catalyzer, all can obtain bromobenzene or contain various substituent bromobenzene.
One, the preparation method of aniline of the present invention and derivative thereof comprises the steps:
1) substituent of benzene and benzene and bromine react derivative and the HBr that generates bromobenzene and bromobenzene under the effect of catalyzer;
2) bromobenzene and the derivative and the NH of step 1) generation
3Or (NH
4)
2CO
3Or NH
4HCO
3Or organic one-level or secondary amine and metal oxide form the metal bromide of metal bromide, ammonia or amine complexing simultaneously or/and the metal hydroxides reaction generates aniline or anils.Step 1) is narrated above-mentioned.Step 2) bromobenzene and derivative and NH in
3Or (NH
4)
2CO
3Or NH
4HCO
3Or organic one-level or secondary amine and metal oxide are or/and the metal hydroxides reaction, the metal oxide that also can further be added with auxiliary agent or load reacts and generates aniline or anils, forms the metal bromide of metal bromide, ammonia or amine complexing simultaneously.The product that step 1) generates can be isolated product bromobenzene or bromobenzene substituent, HBr and not have the reactant benzene or the benzene derivative of complete reaction with distillating method; Benzene or benzene derivative send back to the bromination step utilization, and it is bromine that HBr sends to bromine regeneration reactor oxidation regeneration, and bromobenzene or bromobenzene derivative are used for step 2) synthetic aniline or anils.Step 2) reaction can be that operate continuously is reinforced, also can be the batchwise operation process, and order of addition(of ingredients) can change arbitrarily, is not limited to certain order.Bromobenzene and bromobenzene substituent can while and NH
3Or derivative of ammonia (primary amine or secondary amine) or (NH
4)
2CO
3, or NH
4HCO
3, and metal oxide is or/and the metal hydroxides reaction also can be bromobenzene and substituent elder generation and NH
3Or amine reaction, then reaction mixture again with reactive metal oxide.Step 2) can be with pure bromobenzene, bromobenzene derivative, also can be with their solution.Said ammonia or organic amine are ammonia or organic amine itself or their carbonate, and can decompose other salt that produces ammonia or amine after the heating.Can or have a kind of organic amine that is selected from one-level, secondary amine at least with pure ammonia, can be reactant with their solution also.The derivative of said ammonia is meant all a hydrogen atom and a primary amine and the secondary amine more than the hydrogen atom, organic amine compound are being arranged on the nitrogen-atoms.NH
3Also can be with resolving into NH
3(NH
4)
2CO
3Or NH
4HCO
3Replace.Said metal oxide, metal hydroxides are meant the oxide compound of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, Gd or/and oxyhydroxide, and the mixture of their oxide compound and/or oxyhydroxide.Said auxiliary agent is meant that its effect that is added in the metal oxide is easier the carrying out of reaction that makes bromobenzene and substituent and ammonia or amine and active metal oxide, work the metal bromide be similar to katalysis or make generation and become easier carrying out in the process of metal oxide, those metals, metallic salt, metal oxide, metal hydroxides more completely when reclaiming bromine simple substance at oxidation regeneration.Concrete said auxiliary agent is meant: the vitriol of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, V, Cr, Mn, Sc, Y, La, Sm, Tb, Ce, Fe, Co, Ni, Cu, Zn, Cd, Tm, Yb, Ru, Pr, Dy, Ho, Nd, Eu, Gd, Ag, phosphoric acid salt, carbonate, fluorochemical, muriate, bromide, iodide, silicate, borate, silico-aluminate, phosphomolybdate, phospho heteropoly tungstate, their oxide compound, oxyhydroxide, and the mixture of above compound.Said metal promoter is Rh, Pd, Ir, Pt and Au, and their mixture.In the carrier in the metal oxide of said metal oxide and load, some metal oxide or carrier can play active metal oxide, simultaneously also can play carrier, prevent metal oxide and bromide grain growth, to guarantee the high reactivity and the reproducibility of metal oxide active ingredient, they have a kind of TiO of being selected from least
2, B
2O
3, ZrO
2, HfO
2, Nb
2O
5, Ta
2O
5, MoO
3, WO
3, SiO
2, CeO
2Said metal oxide-loaded in, carrier is selected from TiO
2, ZrO
2, HfO
2, Nb
2O
5, Ta
2O
5, MoO
3, WO
3, CeO
2, SiO
2, GeO
2, B
2O
3, Al
2O
3, activated carbon, and their mixture.Step 2) temperature of reaction is from 50 ℃ to 450 ℃, better is 80 ℃ to 400 ℃, preferably 100 ℃ to 350 ℃.Step 2) reaction pressure is from 0.1 normal atmosphere to 400 normal atmosphere, and pressure range is 0.5 normal atmosphere to 350 normal atmosphere preferably, preferably 1 normal atmosphere to 300 normal atmosphere.Step 2) react by stoichiometric coefficient of chemical reaction between each reactant in, but the amount of certain reactant can be suitably some more.Except bromobenzene and derivative and NH
3Or (NH
4)
2CO
3Or NH
4HCO
3Or organic one-level or secondary amine are as outside the reactant, said metal oxide, metal hydroxides in reaction also as reactant, but it is special reactant, be to participate in reaction as the catalyzed reaction agent, and amount is by the stoichiometric coefficient of chemical reaction supply, not being a small amount of, is the reagent with katalysis, and the reaction of participation promptly itself is arranged.Metal ammonia or amine complex and other metallic compound solid fractionation by distillation go out organic product and the reactant that not have to have reacted after, behind thermal degradation recovery ammonia, amine, remaining metal bromide obtains metal oxide and bromine through oxidation regeneration.Step 2) the liquids mutually available fractionation by distillation product aniline that generates of reaction back and derivative thereof, reactant, and water.Step 2) the solids phase of Sheng Chenging can reclaim NH with the water vapor purging method of heating
3, the aniline of absorption or anils, the reactant benzene of complete reaction not, benzene derivative and water; These purging desorption things are merged in distillation tower to be separated; The NH that reclaims
3Can be reused, the benzene of recovery and benzene derivative can be reused; Remaining at last mineral compound.Last mineral compound will be regenerated as metal oxide and reclaim bromine by dioxygen oxidation; Metal oxide and bromine can be recycled.Metal oxide and metal hydroxides can prepare with one of following several method: 1) metallic salt coprecipitation method preparation; 2) metallic salt mixture thermolysis, or with pickling process metallic salt, comprising active metal oxide, oxyhydroxide, and the presoma of auxiliary agent, be carried on the carrier, drying is carried out thermolysis more then, makes purpose oxide compound or oxyhydroxide.In the preparation process of purpose oxide compound, may adopt diverse ways to carry out in drying and the high temperature air to presoma or calcination disaggregating treatment in the oxygen; These treating processess comprise top described content, but are not limited to top described scope.Step 2) amount of auxiliary agent accounts for 0.01%～10% of entire reaction thing gross weight in.Carrier, got final product 1: 99 or 99: 1 or/and the amount of metal hydroxides ratio is arbitrary proportion with the reactant metal oxide; Carrier is arbitrary proportion with the amount ratio of auxiliary agent, gets final product preferred 1: 0.1～10 1: 99 or 99: 1.
Two, the preparation method of phenol derivmives blend biology of the present invention comprises the steps:
1) substituent of benzene and benzene and bromine react derivative and the HBr that generates bromobenzene and bromobenzene under the effect of catalyzer;
2) bromobenzene of step 1) generation and derivative thereof and water and metal oxide are or/and the metal hydroxides reaction generates phenol or phenol derivatives and metal bromide.Step 1) is narrated above-mentioned.Step 2) bromobenzene in and derivative and water and metal oxide be or/and metal hydroxides reaction, also further is added with carrier loaded metal oxide, oxyhydroxide and auxiliary agent and reacts and generate phenol or phenol derivatives and metal bromide.Step 2) reaction can be that operate continuously is reinforced, also can be the batchwise operation process, and order of addition(of ingredients) can change arbitrarily, is not limited to certain order.Step 2) metal oxide in is or/and metal hydroxides is meant that the oxide compound of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, Gd is or/and oxyhydroxide, and their mixture, and they and SiO
2, B
2O
3Mixture.Can be with pure bromobenzene, bromobenzene derivative, also can be with their solution.Said auxiliary agent is selected from following 1) and 2) in metal oxide, oxyhydroxide, salt, carbonate, phosphoric acid salt, vitriol, muriate, fluorochemical, bromide, iodide as metal, the halogenide of Ru, Rh, Pd, Ir, Pt, Ag, Au, oxide compound, oxyhydroxide, their salt, and the mixture of above metal and nonmetal compound, these auxiliary agents work to accelerate bromobenzene and the hydrolysis of bromobenzene derivative; Wherein auxiliary agent 1): the vitriol of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, V, Cr, Mn, Sc, Y, La, Sm, Tb, Ce, Fe, Co, Ni, Cu, Zn, Cd, Tm, Yb, Ru, Pr, Dy, Ho, Nd, Eu, Gd, Ag, phosphoric acid salt, carbonate, fluorochemical, muriate, bromide, iodide, silicate, borate, silico-aluminate, phosphomolybdate, phospho heteropoly tungstate, their oxide compound, oxyhydroxide, and the mixture of above compound; Auxiliary agent 2): metal promoter is Rh, Pd, Ir, Pt and Au, and their mixture.In the carrier in the metal oxide of said metal oxide and load, some metal oxide or carrier can play active metal oxide, simultaneously also can play carrier, prevent metal oxide and bromide grain growth, to guarantee the high reactivity and the reproducibility of metal oxide active ingredient, they have a kind of TiO of being selected from least
2, B
2O
3, ZrO
2, HfO
2, Nb
2O
5, Ta
2O
5, MoO
3, WO
3, SiO
2, CeO
2Said metal oxide-loaded in, its carrier is selected from TiO
2, ZrO
2, HfO
2, Nb
2O
5, Ta
2O
5, MoO
3, WO
3, CeO
2, SiO
2, SnO
2, GeO
2, Bi
2O
3, Al
2O
3, activated carbon, and their mixture.Step 2) temperature of reaction is from 50 ℃ to 450 ℃, better is 80 ℃ to 400 ℃, preferably 100 ℃ to 350 ℃.Step 2) reaction pressure is from 0.1 normal atmosphere to 400 normal atmosphere, and pressure range is 0.5 normal atmosphere to 350 normal atmosphere preferably, preferably 1 normal atmosphere to 300 normal atmosphere.Step 2) react by stoichiometric coefficient of chemical reaction between each reactant in, but the amount of certain reactant can be suitably some more.Except bromobenzene and derivative and water as the reactant, said metal oxide, metal hydroxides in reaction also as reactant, but it is special reactant, be to participate in reaction as the catalyzed reaction agent, and amount is by the stoichiometric coefficient of chemical reaction supply, not being a small amount of, is the reagent with katalysis, and the reaction of participation promptly itself is arranged.Step 2) obtain a mixture after having reacted, adopt underpressure distillation, separate the bromobenzene or the bromobenzene substituent that haunt and reacted, phenol or phenol substituent, water, remaining is metal bromide and hopcalite.The bromide of some metal can oxidation be got back to metal oxide in air or in the oxygen, and these metal oxides or bromide are called as actives; In reaction, perhaps also exist with metal hydroxides owing to reacting with water; These metals comprise Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, Dy, V, Cr, Yb, Tm, Mn, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, Gd; More than the oxide compound or the oxyhydroxide of these metals in reaction, play active specy.Step 2) mixture of Sheng Chenging also can adopt spray-drying process to separate; In this process, water is arranged in the steam, do not have organic reactant, the product phenols of complete reaction, they will be separated in separation column; Isolated water and organic reactant can be utilized again; Remaining at last mineral compound.Mineral compound is metal oxide and metal bromide; They are in oxidation reactor, and with oxygen in oxygen or the air, oxidation regeneration is metal oxide and is regenerated as Br
2Metal oxide and metal hydroxides can prepare with one of following several method: the preparation of available metal salt coprecipitation method, or metallic salt mixture thermolysis preparation, or with pickling process metallic salt be carried on the carrier, then dry, go thermolysis again, make purpose metal oxide or metal hydroxides.In the preparation process of purpose metal oxide or metal hydroxides, can adopt diverse ways that presoma is carried out drying, comprise in oven dry, vacuum-drying and the high temperature air or in the oxygen or calcination decomposition etc. in other special gas; These treating processess comprise these claims scope, but are not limited to these claims declared range.Step 2) amount of auxiliary agent accounts for 0.01%～10% of entire reaction thing gross weight in.Carrier, got final product 1: 99 or 99: 1 or/and the amount of metal hydroxides ratio is arbitrary proportion with the reactant metal oxide; Carrier is arbitrary proportion with the amount ratio of auxiliary agent, gets final product preferred 1: 0.1～10 1: 99 or 99: 1.
Three, the preparation method of coproduction aniline of the present invention and phenol derivmives blend biology comprises the steps:
1) substituent of benzene and benzene and bromine react derivative and the HBr that generates bromobenzene and bromobenzene under the effect of catalyzer;
2) bromobenzene of step 1) generation and derivative thereof and ammoniacal liquor or volatile salt or ammonium bicarbonate aqueous solution and metal oxide are or/and the metal hydroxides reaction generates the mixture of aniline or anils and phenol or phenol derivatives, generate the metal bromide that metal bromide and ammino close in the reaction, generated the metal bromide that metal bromide and ammino close in the reaction.Step 1) is narrated above-mentioned.Step 2) bromobenzene in and derivative and with ammoniacal liquor or volatile salt or ammonium bicarbonate aqueous solution and metal oxide or/and the metal hydroxides reaction, be added with further also that carrier loaded metal oxide, oxyhydroxide and auxiliary agent react and the mixture that generates aniline or anils and phenol or phenol derivatives has generated the metal bromide that metal bromide and ammino close in the reaction.Step 2) reaction can be batch-wise still reaction or successive reaction, and the order of addition(of ingredients) of reactant can change arbitrarily.Step 2) reaction can be with pure bromobenzene, bromobenzene derivative, also can be with their solution.Step 2) ammoniacal liquor in the reaction also can change (NH into
4)
2CO
3Or NH
4HCO
3The aqueous solution.The ammoniacal liquor of reactant step 2), wherein the ratio of ammonia and water can be an arbitrary proportion, and high density ammoniacal liquor can be depressed preparation adding, ratio can be from 1: 99 to 99: 1; It influences the ratio of amine and phenol in the product than regular meeting; In the actual production, the aniline that can be as required or the ratio of aniline substituent and phenol or phenol substituent are determined ammonia concn.Said metal oxide, metal hydroxides is meant the oxide compound of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, Gd or/and oxyhydroxide, and the mixture of their oxide compound, oxyhydroxide.Said auxiliary agent be meant above-mentioned in the assorted step 2 of vitriol, phosphoric acid salt, carbonate, fluorochemical, muriate, bromide, iodide, silicate, borate, silico-aluminate, phosphomolybdate, phosphorus tungsten of listed metal) temperature of reaction is from 50 ℃ to 450 ℃, better be 80 ℃ to 400 ℃, preferably 100 ℃ to 350 ℃.Step 2) reaction pressure is from 0.1 normal atmosphere to 400 normal atmosphere, and pressure range is 0.5 normal atmosphere to 350 normal atmosphere preferably, preferably 1 normal atmosphere to 300 normal atmosphere.Step 2) react by stoichiometric coefficient of chemical reaction between each reactant in, but the amount of certain reactant can be suitably some more.Except bromobenzene and derivative and ammoniacal liquor or volatile salt or ammonium bicarbonate aqueous solution as the reactant, said metal oxide, metal hydroxides in reaction also as reactant, but it is special reactant, be to participate in reaction as the catalyzed reaction agent, and amount is by the stoichiometric coefficient of chemical reaction supply, not being a small amount of, is the reagent with katalysis, and the reaction of participation promptly itself is arranged.Step 2) aniline (or anils) is arranged in the product, phenol (or phenol derivatives), the bromobenzene that has not reacted (bromobenzene derivative), ammonia, water, and metallic compound and carrier and auxiliary agent (inorganics); Product is organic product, the reactant that has not reacted and water in the gas phase through spray evaporation, and they can feed separation column and separate; Solid phase is a metal oxide, metal hydroxides, metal bromide and carrier and auxiliary agent.Step 2) aniline in the product (or anils), phenol (or phenol derivatives), the bromobenzene (bromobenzene derivative), ammonia, the water that have not reacted, also available underpressure distillation separates, remaining inorganic solid compounds.It is that metal oxide and bromine recycle in the flow process that remaining inorganic solid compounds will be placed in the interior oxidation regeneration of regeneration reactor.Inorganic solid compounds also can be regenerated as metal oxide and bromine with dioxygen oxidation in oxygen or the air in the oxidation regeneration reactor.The preparation of said load metal oxide and oxyhydroxide, metal oxide, oxyhydroxide preparation, and the preparation that contains metal oxide, the oxyhydroxide of auxiliary agent can adopt method of describing in above-mentioned " preparation method of phenol derivmives blend biology ", but is not limited to top said method.Step 2) amount of auxiliary agent accounts for 0.01%～10% of entire reaction thing gross weight in.Carrier, got final product 1: 99 or 99: 1 or/and the amount of metal hydroxides ratio is arbitrary proportion with the reactant metal oxide; Carrier is arbitrary proportion with the amount ratio of auxiliary agent, gets final product preferred 1: 0.1～10 1: 99 or 99: 1.
As from the foregoing, the present invention is by benzene and contains various substituent benzene and at first obtain bromobenzene with bromine reaction and contain various substituent bromobenzenes.Again with bromobenzene or contain various substituent bromobenzenes and the reaction of metal oxide and/or metal hydroxides generates aniline or contains various substituent anilss.Also can with bromobenzene or contain various substituent bromobenzenes and metal oxide or/and metal hydroxides and H
2The O reaction generates phenol or contains various substituent phenol derivativess.With concrete reaction formula preparation process of the present invention is described again below:
M(NH
3)
mBr
n??+H
2O
M(NH
3)
mBr
n??+H
2O
M(NH
3)
mBr
n??+H
2O
In said process, reaction has produced HBr, MBr
nOr/and M (NH
3)
mBr
n, wherein m, n represent number.Wherein HBr is regenerated as Br with air or oxygen through catalytic oxidation
2, MBr
nOr/and M (NH
3)
mBr
nReclaim NH earlier through thermal degradation
3, remaining MBr
nBe regenerated as metal oxide and Br through oxygen or atmospheric oxidation
2, they can recycle for subsequent process.X in the above-mentioned phenyl ring
1, X
2Represent substituting group, as hydrogen, chlorine, fluorine, bromine, phenyl, alkyl, thiazolinyl, alkynyl, nitro, sulfo group, phenylol, thiophenol base, anilino etc., MO
xIn, M refers to metals such as Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, Gd, and x represents the number of O.
Net result is to consume benzene or benzene substituent, ammonia, oxygen to generate aniline or aniline substituent, water during synthetic aniline in above process, water and aniline or aniline substituent can be by fractionation by distillation, wherein bromine and metal oxide can be recycled, the discharging of non-environmental-pollution thing.
In phenol or phenol substituent were synthetic, net result was to consume benzene or benzene substituent and oxygen, generates phenol and phenol substituent.Bromine and metal oxide can be recycled.
In above synthetic aniline, aniline substituent, phenol, phenol substituent process, the reaction conditions gentleness does not have the byproduct of the difficult pin in market to generate (the acetone generation that waits the mol amount is arranged during traditional phenol is synthetic).And the raw material valency that is adopted is low, the synthetic aniline high HNO of valency of traditional process
3, hydrogen; The synthetic middle O that uses here with propylene of tradition phenol
2And H
2O.No unmanageable waste liquid generates in the reaction, and in traditional oil of mirbane method, nitrifying process will be made catalyzer with the vitriol oil, thereby but nitrifying process generation water makes sulfuric acid thinning, and can not the continuation effect.
The present invention compares with the method for existing synthetic aniline, has very outstanding advantage: 1) high benzene transformation efficiency (＞95%); 2) high aniline selectivity (＞95%); 3) temperature of reaction is 200 ℃, and reaction pressure also has only 80 normal atmosphere; 4) whole synthetic route only consumes benzene NH
3And O
2, other raw materials used can regeneration.Therefore, the present invention also can regard as a kind of particular form by benzene and NH
3The method of the synthetic aniline of direct reaction; 5) characteristics of maximum of the present invention are with bromobenzene and NH
3And reactive metal oxide makes aniline.This reaction is a kind of brand-new reaction; 6) whole synthetic route does not have environmental pollution.The present invention bromobenzene and H
2O and reactive metal oxide make phenol, are a kind of brand-new reaction systems.The raw material that is consumed in the whole synthetic route is benzene, H
2O and O
2, other raw material that relates to is all renewable to be reused.
Embodiment:
Describe the present invention below in conjunction with embodiment:
Embodiment
1, Ti formulations prepared from solutions
Take by weighing 75.6g oxalic acid and be dissolved in the 300ml water, be heated to 60 ℃, under violent stirring, slowly drip the 68ml tetra-n-butyl titanate.Obtain a clear solution this moment.After leaving standstill, there is one deck yellow oily liquid on the upper strata, inhales with suction pipe and goes.Add water again to 400ml.So just obtain the mixing solutions of 1.5M oxalic acid+0.5M tetra-n-butyl titanate.
2, the preparation of metal oxide
With 12g Cu (NO
3)
2H
2O is dissolved in 20ml H
2Among the O, add the polyacrylic acid solution (molecular-weight average is 2000) of 40ml 30%.After stirring this solution slowly is added drop-wise in the above-mentioned Ti solution of 100ml.Obtain light green colloidal solution like this.This colloidal solution is moved in the retort furnace after 8 hours in 110 ℃ of heating, and the temperature of retort furnace was raised to 500 ℃ by room temperature in 4 hours, 500 ℃ keep 5 hours after naturally cooling.The greyish-green solid that obtains so promptly makes CuO/TiO required for the present invention after grinding
2Mixed metal oxide.
3, the preparation of bromobenzene
1) in 20ml benzene, adds the 0.5g reduced iron powder, fully stir under the room temperature, slowly drip the 4ml bromine.Added Br in 10 minutes
2After, continue to stir 20 minutes, be warmed up to 60 ℃, insulation 4h.Place and get colourless liquid after 2 days.Add 10ml 10%NaOH, stir.Separate upper water solution, lower floor's liquid is the benzole soln of bromobenzene.Gas chromatographic analysis shows that the bromobenzene selectivity that makes is more than 97%.
2) in 20ml benzene, add 0.5g ZrO
2(handling through the vitriol oil) fully stirs under the room temperature, slowly drips the 4ml bromine.Added Br in 15 minutes
2After, continue to stir 25 minutes, be warmed up to 105 ℃, insulation 4h.Place and get colourless liquid after 2 days.Add 10ml10%NaOH, stir.Separate upper water solution, lower floor's liquid is the benzole soln of bromobenzene.Gas chromatographic analysis shows that the bromobenzene selectivity that makes is more than 95%.
4, the preparation of aniline
(1) prepares aniline with the 100ml autoclave that is lined with the Teflon layer.Add 13g embodiment 2 prepared metal oxides, 10ml bromobenzene and 20ml liquid NH in this still
3The temperature of reactor was risen to 180 ℃ by room temperature in 80 minutes.And keep 180 ℃ of 4h so that react completely.In this process, the still internal pressure is at 65～80 normal atmosphere.Having only the bromobenzene of 2.4% (molar percentage) not have reaction in the product that makes like this is that the transformation efficiency of bromobenzene is 97.6%.As the aniline selectivity, then this selectivity is 94.7% as if the ratio that accounts for product (mixture of aniline and benzene) with aniline.
(2) the stainless steel autoclave that polishes with 100ml, add 11g embodiment 2 prepared metal oxides, 10ml bromobenzene and 20ml liquefied ammonia in the reactor, in 80 minutes, the still temperature is risen to 200 ℃ by room temperature, and be incubated 4 hours so that react completely at 200 ℃.Pressure in this process in the reactor is 70～80 normal atmosphere.The transformation efficiency of bromobenzene is 87% in the product that makes like this, and the selectivity of aniline is 92%.
(3) the stainless steel autoclave that polishes with 100ml.Add 13g embodiment 2 prepared metal oxides, 10ml bromobenzene and 20ml liquefied ammonia in the reactor.In 80 minutes, the still temperature is risen to 180 ℃ by room temperature.Still internal pressure in this process is 57～75 normal atmosphere.The transformation efficiency of bromobenzene is 84.4% in the product that makes like this, and the selectivity of aniline is 90%.
(4) the stainless steel autoclave that polishes with 100ml.In still, add metal oxide 13g, 10ml bromobenzene, 65ml benzene and the 20ml liquefied ammonia that embodiment 2 makes.In 80 minutes, the still temperature is raised to 220 ℃ by room temperature, and this temperature insulation 4 hours.The still internal pressure is 118～138 normal atmosphere in this process.Has only the intact bromobenzene of aniline, benzene and unreacted in the product that makes like this.The transformation efficiency of bromobenzene is 70%, the selectivity 92.9% of aniline.
(5) the stainless steel autoclave that polishes with 100ml.In still, add metal oxide 13g, 10ml bromobenzene, 6.5ml benzene and the 30ml liquid NH that embodiment 2 makes
3In 80 minutes, the still temperature is raised to 180 ℃ by room temperature, and is incubated 4 hours so that react completely in this temperature.Still internal pressure in this process is 112～120 normal atmosphere.Have only aniline, benzene and not reacted bromobenzene in the product that makes like this.The transformation efficiency of bromobenzene is 40%, and the selectivity of aniline is 95%.
(6) with the 100ml stainless steel autoclave that polishes.In still, add metal oxide 13g, 10ml bromobenzene, 7ml benzene and the 15ml liquefied ammonia that makes in the embodiment 2.In 80 minutes, the still temperature is raised to 180 ℃ by room temperature, and this temperature insulation 4 hours.Still internal pressure in this process is 33～37 normal atmosphere.Have only aniline, benzene and unreacted bromobenzene in the product that makes like this.The transformation efficiency of bromobenzene is 10%, and the productive rate of aniline is 9%, and the selectivity of aniline is 90%.
(7) with unpolished 100ml stainless steel autoclave (its inwall may be impregnated with metals such as Ru, Ni).In still, add metal oxide 11g, bromobenzene 10ml and the 20ml liquid NH that makes in the embodiment 2
3The still temperature was raised to 200 ℃ by room temperature in 80 minutes, and kept 4 hours in this temperature.The still pressure of this process is 67～80 normal atmosphere.The transformation efficiency of bromobenzene is 95% in the product that obtains like this, and selectivity is 71.6%, and its by product is a benzene.
(8) with unpolished 100ml stainless steel autoclave.In still, add metal oxide 11g, 10ml bromobenzene and the 10ml liquefied ammonia that makes in the embodiment 2.The still temperature was raised to 200 ℃ by room temperature in 80 minutes, and kept 4 hours in this temperature.Still internal pressure in this process is 34～37 normal atmosphere.The transformation efficiency of bromobenzene is 62% in the product that obtains like this, and selectivity is 69.3%.Its by product is a benzene.
5, the regeneration of metal oxide
In the final product of aniline preparation process, heating earlier obtains respectively: the 1. intact NH of unreacted
3And the NH that is decomposed to form of the ammonia complex of metal
3, these NH
3Can reuse; 2. the intact bromobenzene of unreacted also can reuse; 3. benzene can reuse and make bromobenzene; 4. product aniline, at last Sheng Xia solid part in retort furnace in 350 degree heating 4 hours, the Br of generation
2Can reuse and be used for preparing bromobenzene, remaining solid is the regenerated metal oxide.It can be used as preparation aniline again and uses.
6, the reactive behavior of regenerated metal oxide is investigated
(1) in the stainless steel reactor of 2.5ml, adds metal oxide, 0.25ml bromobenzene and the 0.45g volatile salt that 0.25g makes by embodiment 2.Temperature of reaction is 210 ℃.Reaction times is 4 hours.Each reaction finishes the back and carries out the regeneration of metal oxide by embodiment 5.The regenerated metal oxide is used as reactant next time like this.Seven secondary responses have been carried out so altogether.Its experimental result such as following table 1:
Table 1
| The n secondary response | The bromobenzene transformation efficiency | The aniline selectivity |
| 1 | ?99％ | 92％ |
| 2 | ?100％ | 90％ |
| 3 | ?99％ | 92％ |
| 4 | ?100％ | 91％ |
| 5 | ?100％ | 92％ |
| 6 | ?100％ | 91％ |
| 7 | ?100％ | 93％ |
As seen, metal oxide can carry out repeated regeneration by embodiment 5 and utilized.
(2) repeatedly the activity of regenerated metal oxide and freshly prepd metal oxide specific activity be.
In I 2.5ml stainless steel reactor, add and press the prepared metal oxide 0.25g of embodiment 2,0.25ml bromobenzene and 0.45g volatile salt.
In II 2.5ml stainless steel reactor, add by metal oxide 0.25g, 0.25ml bromobenzene and 0.45g carbonic acid after the embodiment 5 methods regeneration seven times and press.
I and two reactors of II were reacted 4 hours at 190 ℃ simultaneously.The product that obtains is as shown in table 2 below:
Table 2
| Reactor I | Reactor II | |
| The bromobenzene transformation efficiency | 25％ | 100％ |
| The aniline selectivity | 80％ | 93％ |
As seen, higher through seven regenerated metal oxides than the metal oxide activity of prepared fresh.This regeneration that shows the metal oxide that relates in the synthetic route of the present invention is more conducive to down secondary response.Be that metal oxide its reactive behavior after regeneration is improved.
7, various different metal oxides specific activitys
Respectively with identical stoichiometric various different metal oxides and 0.25ml bromobenzene and 0.45g volatile salt 210 ℃ of reactions 4 hours.The result shows that the reactive behavior of various different metal oxides successively decreases in the following order:
Press the CuO/TiO of embodiment 2 preparations
2～CuO/TiO
2/ Y
2O
3(mol ratio 10: 10: 1)～CuO/TiO
2/ Al
2O
3(mol ratio 10: 10: 1)＞pure CuO～Y
2O
3＞NiO＞Co
2O
3＞MnO
2～La
2O
3～Bi
2O
3～CaO～Bao～ZnO～MO
2O
3～Cr
2O
3～Fe
2O
3～MgO
8, the coproduction of aniline and phenol
In the stainless steel reactor of 2.5ml, add 0.15gCuO powder, 0.25ml bromobenzene and 0.25ml ammoniacal liquor, in 220 ℃ of reactions 4 hours.Experimental result shows: the transformation efficiency of bromobenzene is 100%, and phenol yield is 30%, and the aniline productive rate is 25%, and other has 45% benzene generation.
9, the circulation ratio for preparing aniline reaction by bromobenzene
In 8 identical 2.5ml stainless steel reactors, respectively add the CuO/TiO that 0.45g volatile salt, 0.25ml bromobenzene and 0.25g make by embodiment 2
2, respectively reacted 4 hours in 210 ℃.Result such as following table 3:
Table 3
| The reactor sequence number | The bromobenzene transformation efficiency | The aniline productive rate |
| 1 | ?100％ | 75％ |
| 2 | ?100％ | 72％ |
| 3 | ?100％ | 70％ |
| 4 | ?100％ | 75％ |
| 5 | ?100％ | 73％ |
| 6 | ?100％ | 70％ |
| 7 | ?100％ | 73％ |
| 8 | ?100 | 72％ |
The above results shows, the prepared in reaction aniline of bromobenzene and metal oxide, volatile salt, and the circulation ratio of its product is fine.
10, prepare phenol by bromobenzene
In the 2.5ml stainless steel reactor, add metal oxide 0.5g, bromobenzene 0.3ml and the H that makes by embodiment 2
2O1.0ml.240 ℃ of reactions 4 hours.The result shows the transformation efficiency 33% of bromobenzene in the product, the productive rate 17% of phenol.By product is a benzene.
Claims (97)
1, the preparation method of a kind of aniline and derivative thereof comprises the steps:
1) substituent of benzene and benzene and bromine react derivative and the HBr that generates bromobenzene and bromobenzene under the effect of catalyzer;
2) bromobenzene and the derivative and the NH of step 1) generation
3Or (NH
4)
2CO
3Or NH
4HCO
3Or organic one-level or secondary amine and metal oxide form the metal bromide of metal bromide, ammonia or amine complexing simultaneously or/and the metal hydroxides reaction generates aniline or anils.
2, a kind of preparation method of phenol derivmives blend biology comprises the steps:
1) substituent of benzene and benzene and bromine react derivative and the HBr that generates bromobenzene and bromobenzene under the effect of catalyzer;
2) bromobenzene of step 1) generation and derivative thereof and water and metal oxide are or/and the metal hydroxides reaction generates phenol or phenol derivatives and metal bromide.
3, the preparation method of a kind of coproduction aniline and phenol derivmives blend biology comprises the steps:
1) substituent of benzene and benzene and bromine react derivative and the HBr that generates bromobenzene and bromobenzene under the effect of catalyzer;
2) bromobenzene of step 1) generation and derivative thereof and ammoniacal liquor or volatile salt or ammonium bicarbonate aqueous solution and metal oxide are or/and the metal hydroxides reaction generates the mixture of aniline or anils and phenol or phenol derivatives, generate the metal bromide that metal bromide and ammino close in the reaction, generated the metal bromide that metal bromide and ammino close in the reaction.
4, the preparation method of aniline according to claim 1 and derivative thereof is characterized in that step 1) hydrogen bromide HBr reclaims bromine through oxidation.
5, the preparation method of aniline according to claim 1 and derivative thereof is characterized in that the said catalyzed reaction of step 1) can be a heterogeneous catalytic reaction, also can be homogeneous catalytic reaction.
6, the preparation method of aniline according to claim 1 and derivative thereof, the reaction that it is characterized in that the said benzene of step 1) or benzene derivative and bromine can be that the reaction of operate continuously also can be a still formula batch reactions.
7, the preparation method of aniline according to claim 1 and derivative thereof, it is characterized in that said step 1) reaction can be benzene or benzene derivative and bromine charging simultaneously, also can be one earlier after one, or a reactant once adds, another reactant adds in batches or continuously.
8, the preparation method of aniline according to claim 1 and derivative thereof is characterized in that the reaction of said step 1) can carry out between-40 ℃ to 550 ℃, service temperature is-20 ℃ to 450 ℃ preferably, and best service temperature is-20 ℃ to 300 ℃.
9, the preparation method of aniline according to claim 1 and derivative thereof, it is characterized in that said step 1) reaction pressure is between 0.1 normal atmosphere to 300 normal atmosphere, pressure range is between 0.5 normal atmosphere to 200 normal atmosphere preferably, preferably between 0.8 normal atmosphere to 50 normal atmosphere.
10, the preparation method of aniline according to claim 1 and derivative thereof, the substituent that it is characterized in that the said benzene of step 1) comprises chloro thing, fluoro thing, bromo-derivative, phenyl substituent, alkyl substituent, alkenyl substituted thing, alkynyl substituted thing, nitro substituent, sulfo group substituent, phenylol substituent, thiophenol base substituent, the anilino substituent of benzene.
11, the preparation method of aniline according to claim 1 and derivative thereof is characterized in that step 2) middle bromobenzene and derivative and NH
3Or (NH
4)
2CO
3Or NH
4HCO
3Or organic one-level or secondary amine and metal oxide are or/and the metal hydroxides reaction, the metal oxide that also further is added with auxiliary agent or load reacts and generates aniline or anils, forms the metal bromide of metal bromide, ammonia or amine complexing simultaneously.
12, the preparation method of aniline according to claim 1 and derivative thereof, it is characterized in that step 2) in metal ammonia or amine complex and other metallic compound solid fractionation by distillation go out organic product and the reactant that do not have to have reacted after, after thermal degradation reclaimed ammonia, amine, remaining metal bromide obtained metal oxide and bromine through oxidation regeneration.
13, the preparation method of aniline according to claim 1 and derivative thereof is characterized in that the described catalyzer of step 1) is metal oxide, metal chloride, metal fluoride, metal iodide, metal sulfate, metal phosphate, metal heteropolyacid salt, BF
3, the metal except that iron powder, and the arbitrary proportion mixture of above-listed compound.
14, the preparation method of aniline according to claim 1 and derivative thereof is characterized in that product that step 1) generates can isolate product bromobenzene or bromobenzene substituent, HBr and not have the reactant benzene or the benzene derivative of complete reaction with distillating method; Benzene or benzene derivative send back to the bromination step utilization, and it is bromine that HBr sends to bromine regeneration reactor oxidation regeneration, and bromobenzene or bromobenzene derivative are used for step 2) synthetic aniline or anils.
15, the preparation method of aniline according to claim 1 and derivative thereof is characterized in that the said catalyzer of step 1) can be homogeneous catalyst or heterogeneous catalyst.
16,, it is characterized in that the described catalyzer of step 1) can be loaded catalyst or unsupported catalyst according to the preparation method of claim 13 or 15 described aniline and derivative thereof.
17, the preparation method of aniline according to claim 16 and derivative thereof is characterized in that said loaded catalyst contains a kind of mutually active and carrier of being made up of one or more metallic compounds of mixture.
18, the preparation method of aniline according to claim 17 and derivative thereof is characterized in that said carrier is meant to have a kind of being selected from as SiO at least
2, B
2O
3, Al
2O
3, GeO
2, TiO
2, ZrO
2, Nb
2O
5, Ta
2O
5, activated carbon etc. metallic compound or nonmetal or nonmetallic compound.
19, the preparation method of aniline according to claim 17 and derivative thereof, it is characterized in that said activity of such catalysts is Li mutually, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Gr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, the oxide compound of Gd, fluorochemical, muriate, bromide, iodide, phosphoric acid salt, vitriol, carbonate, silicate, borate, and their mixture or their mixture and Ru, Rh, Pd, Ir, Pt, Ag, the mixture of metals such as Au and metallic compound.
20, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that step 2) in bromobenzene and bromobenzene substituent can be simultaneously and NH
3Or derivative of ammonia (primary amine or secondary amine) or (NH
4)
2CO
3, or NH
4HCO
3, and metal oxide is or/and the metal hydroxides reaction also can be bromobenzene and substituent elder generation and NH
3Or amine reaction, then reaction mixture again with reactive metal oxide.
21, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that step 2) reaction can be that operate continuously is reinforced, also can be the batchwise operation process, order of addition(of ingredients) can change arbitrarily, is not limited to certain order.
22, preparation method according to claim 1 or 10 described aniline and derivative thereof, it is characterized in that step 2) in said metal oxide, metal hydroxides is meant Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, the oxide compound of Gd is or/and oxyhydroxide, and the mixture of their oxide compound and/or oxyhydroxide.
23, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that step 2) in the derivative of said ammonia be meant all a hydrogen atom and a primary amine and the secondary amine more than the hydrogen atom, organic amine compound are being arranged on the nitrogen-atoms.
24, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that step 2) said auxiliary agent is meant those metals, metallic salt, metal oxide, the metal hydroxides that is added in the metal oxide, its effect is easier the carrying out of reaction that makes bromobenzene and substituent and ammonia or amine and active metal oxide, work the metal bromide be similar to katalysis or make generation and become easier carrying out in the process of metal oxide at oxidation regeneration, more thorough when reclaiming bromine simple substance.
25, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that step 2) in the carrier in the metal oxide of said metal oxide and load, some metal oxide or carrier can play active metal oxide, simultaneously also can play carrier, prevent metal oxide and bromide grain growth, to guarantee the high reactivity and the reproducibility of metal oxide active ingredient, they have a kind of TiO of being selected from least
2, B
2O
3, ZrO
2, HfO
2, Nb
2O
5, Ta
2O
5, MoO
3, WO
3, SiO
2, CeO
2
26, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that said metal oxide-loaded in, carrier is selected from TiO
2, ZrO
2, HfO
2, Nb
2O
5, Ta
2O
5, MoO
3, WO
3, CeO
2, SiO
2, GeO
2, B
2O
3, Al
2O
3, activated carbon, and their mixture.
27, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that NH
3Also can be with resolving into NH
3(NH
4)
2CO
3Or NH
4HCO
3Replace.
28, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that step 2) temperature of reaction is from 50 ℃ to 450 ℃, better is 80 ℃ to 400 ℃, preferably 100 ℃ to 350 ℃.
29, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that step 2) reaction pressure is from 0.1 normal atmosphere to 400 normal atmosphere, pressure range is 0.5 normal atmosphere to 350 normal atmosphere preferably, preferably 1 normal atmosphere to 300 normal atmosphere.
30, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that said ammonia or organic amine, is ammonia or organic amine itself or their carbonate, and can decompose other salt that produces ammonia or amine after the heating.
31, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that metal oxide and metal hydroxides can prepare with one of following several method: 1) metallic salt coprecipitation method preparation; 2) metallic salt mixture thermolysis, or with pickling process metallic salt, comprising active metal oxide, oxyhydroxide, and the presoma of auxiliary agent, be carried on the carrier, drying is carried out thermolysis more then, makes purpose oxide compound or oxyhydroxide.
32, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that and can or have a kind of organic amine that is selected from one-level, secondary amine at least with pure ammonia, can with their solution reactant also.
33, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that step 2) can be with pure bromobenzene, bromobenzene derivative, also can be with their solution.
34, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that step 2) react the back liquids mutually available fractionation by distillation product aniline that generates and derivative, reactant, reach water.
35, according to the preparation method of claim 1 or 10 described aniline and derivative thereof, it is characterized in that step 2) the solids phase that generates, can reclaim NH with the water vapor purging method of heating
3, the aniline of absorption or anils, the reactant benzene of complete reaction not, benzene derivative and water; These purging desorption things are merged in distillation tower to be separated; The NH that reclaims
3Can be reused, the benzene of recovery and benzene derivative can be reused; Remaining at last mineral compound.
36, the preparation method of aniline according to claim 24 and derivative thereof, it is characterized in that said auxiliary agent is meant: Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, V, Cr, Mn, Sc, Y, La, Sm, Tb, Ce, Fe, Co, Ni, Cu, Zn, Cd, Tm, Yb, Ru, Pr, Dy, Ho, Nd, Eu, Gd, the vitriol of Ag, phosphoric acid salt, carbonate, fluorochemical, muriate, bromide, iodide, silicate, borate, silico-aluminate, phosphomolybdate, phospho heteropoly tungstate, their oxide compound, oxyhydroxide, and the mixture of above compound.
37, the preparation method of aniline according to claim 24 and derivative thereof is characterized in that said metal promoter is Rh, Pd, Ir, Pt and Au, and their mixture.
38, the preparation method of aniline according to claim 24 and derivative thereof is characterized in that said active metal oxide and oxyhydroxide component are meant that the generation metal bromide is or/and the metal oxide of the metal bromide that ammino closes or oxyhydroxide in the reaction of bromobenzene and derivative and ammonia and derivative thereof; The metal bromide here is or/and the metal bromide that ammino closes can be reproduced into metal oxide and metal hydroxides in heating and oxidative regeneration process, and recovery simple substance bromine and ammonia; These active metal oxide and oxyhydroxide component are oxide compound and the oxyhydroxide of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, Dy, V, Cr, Yb, Tm, Mn, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, Gd, and their mixture.
39, according to the preparation method of claim 31 or 38 described aniline and derivative thereof, it is characterized in that in the preparation process of purpose oxide compound, may adopt diverse ways to carry out in drying and the high temperature air to presoma or calcination disaggregating treatment in the oxygen; These treating processess comprise content described in the claim 38, but are not limited to scope described in the claim 38.
40, the preparation method of aniline according to claim 35 and derivative thereof is characterized in that last mineral compound will be regenerated as metal oxide and reclaim bromine by dioxygen oxidation; Metal oxide and bromine can be recycled.
41, the preparation method of phenol derivmives blend biology according to claim 2 is characterized in that step 1) hydrogen bromide HBr reclaims bromine through oxidation.
42, the preparation method of phenol derivmives blend biology according to claim 2 is characterized in that said step 1) catalyzed reaction can be a heterogeneous catalytic reaction, also can be homogeneous catalytic reaction.
43, the preparation method of phenol derivmives blend biology according to claim 2, the reaction that it is characterized in that said step 1) benzene or benzene derivative and bromine can be that the reaction of operate continuously also can be a still formula batch reactions.
44, the preparation method of phenol derivmives blend biology according to claim 2, it is characterized in that said step 1) reaction can be benzene or benzene derivative and bromine charging simultaneously, also can be one earlier after one, or a reactant once adds, another reactant adds in batches or continuously.
45, the preparation method of phenol derivmives blend biology according to claim 2, it is characterized in that the reaction of said step 1) can carry out between-40 ℃ to 550 ℃, service temperature is-20 ℃ to 450 ℃ preferably, and best service temperature is-20 ℃ to 300 ℃.
46, the preparation method of phenol derivmives blend biology according to claim 2, it is characterized in that said step 1) reaction pressure is between 0.1 normal atmosphere to 300 normal atmosphere, pressure range is between 0.5 normal atmosphere to 200 normal atmosphere preferably, preferably between 0.8 normal atmosphere to 50 normal atmosphere.
47, the preparation method of phenol derivmives blend biology according to claim 2, the substituent that it is characterized in that the said benzene of step 1) comprises chloro thing, fluoro thing, bromo-derivative, phenyl substituent, alkyl substituent, alkenyl substituted thing, alkynyl substituted thing, nitro substituent, sulfo group substituent, phenylol substituent, thiophenol base substituent, the anilino substituent of benzene.
48, the preparation method of phenol derivmives blend biology according to claim 2, it is characterized in that step 2) in bromobenzene and derivative and water and metal oxide or/and the metal hydroxides reaction, also further be added with carrier loaded metal oxide, oxyhydroxide and auxiliary agent and react and generate phenol or phenol derivatives and metal bromide.
49, the preparation method of phenol derivmives blend biology according to claim 2 is characterized in that the described catalyzer of step 1) is metal oxide, metal chloride, metal fluoride, metal iodide, metal sulfate, metal phosphate, metal heteropolyacid salt, BF
3, the metal except that iron powder, and the arbitrary proportion mixture of above-listed compound.
50, the preparation method of phenol derivmives blend biology according to claim 2 is characterized in that the said catalyzer of step 1) can be homogeneous catalyst or heterogeneous catalyst.
51,, it is characterized in that the described catalyzer of step 1) can be loaded catalyst or unsupported catalyst according to the preparation method of claim 49 or 50 described phenol derivmives blend biologies.
52,, it is characterized in that the said loaded catalyst of step 1) contains a kind of mutually active and carrier of being made up of one or more metallic compounds of mixture according to the preparation method of the described phenol derivmives blend biology of claim 51.
53,, it is characterized in that said carrier is meant to have a kind of being selected from as SiO at least according to the preparation method of the described phenol derivmives blend biology of claim 52
2, B
2O
3, Al
2O
3, GeO
2, TiO
2, ZrO
2, Nb
2O
5, Ta
2O
5, activated carbon etc. metallic compound or nonmetal or nonmetallic compound.
54, preparation method according to the described phenol derivmives blend biology of claim 52, it is characterized in that the said activity of such catalysts of step 1) is Li mutually, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Gr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, the oxide compound of Gd, fluorochemical, muriate, bromide, iodide, phosphoric acid salt, vitriol, carbonate, silicate, borate, and their mixture or their mixture and Ru, Rh, Pd, Ir, Pt, Ag, the mixture of metals such as Au and metallic compound.
55, according to the preparation method of claim 2 or 47 described phenol derivmives blend biologies, it is characterized in that step 2) reaction can be that operate continuously is reinforced, also can be the batchwise operation process, order of addition(of ingredients) can change arbitrarily, is not limited to certain order.
56, according to the preparation method of claim 2 or 47 described phenol derivmives blend biologies, it is characterized in that metal oxide or/and metal hydroxides is meant that the oxide compound of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, Gd is or/and oxyhydroxide, and their mixture, and they and SiO
2, B
2O
3Mixture.
57, according to the preparation method of claim 2 or 47 described phenol derivmives blend biologies, it is characterized in that said auxiliary agent is selected from following 1) and 2) in metal oxide, oxyhydroxide, salt, carbonate, phosphoric acid salt, vitriol, muriate, fluorochemical, bromide, iodide as metal, the halogenide of Ru, Rh, Pd, Ir, Pt, Ag, Au, oxide compound, oxyhydroxide, their salt, and the mixture of above metal and nonmetal compound, these auxiliary agents work to accelerate bromobenzene and the hydrolysis of bromobenzene derivative; Auxiliary agent l wherein): the vitriol of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, V, Cr, Mn, Sc, Y, La, Sm, Tb, Ce, Fe, Co, Ni, Cu, Zn, Cd, Tm, Yb, Ru, Pr, Dy, Ho, Nd, Eu, Gd, Ag, phosphoric acid salt, carbonate, fluorochemical, muriate, bromide, iodide, silicate, borate, silico-aluminate, phosphomolybdate, phospho heteropoly tungstate, their oxide compound, oxyhydroxide, and the mixture of above compound; Auxiliary agent 2): metal promoter is Rh, Pd, Ir, Pt and Au, and their mixture.
58, according to the preparation method of claim 2 or 47 described phenol derivmives blend biologies, it is characterized in that in the carrier in the metal oxide of said metal oxide and load, some metal oxide or carrier can play active metal oxide, simultaneously also can play carrier, prevent metal oxide and bromide grain growth, to guarantee the high reactivity and the reproducibility of metal oxide active ingredient, they have a kind of TiO of being selected from least
2, B
2O
3, ZrO
2, HfO
2, Nb
2O
5, Ta
2O
5, MoO
3, WO
3, SiO
2, CeO
2
59, according to the preparation method of claim 2 or 47 described phenol derivmives blend biologies, it is characterized in that said metal oxide-loaded in, its carrier is selected from TiO
2, ZrO
2, HfO
2, Nb
2O
5, Ta
2O
5, MoO
3, WO
3, CeO
2, SiO
2, SnO
2, GeO
2, Bi
2O
3, Al
2O
3, activated carbon, and their mixture.
60, according to the preparation method of claim 2 or 47 described phenol derivmives blend biologies, it is characterized in that step 2) temperature of reaction is from 50 ℃ to 450 ℃, better is 80 to 400 ℃, preferably 100 ℃ to 350 ℃.
61, according to the preparation method of claim 2 or 47 described phenol derivmives blend biologies, it is characterized in that step 2) reaction pressure is from 0.1 normal atmosphere to 400 normal atmosphere, pressure range is 0.5 normal atmosphere to 350 normal atmosphere preferably, preferably 1 normal atmosphere to 300 normal atmosphere.
62, according to the preparation method of claim 2 or 47 described phenol derivmives blend biologies, it is characterized in that can be with pure bromobenzene, bromobenzene derivative, also can be with their solution.
63, according to the preparation method of claim 2 or 47 described phenol derivmives blend biologies, it is characterized in that metal oxide and metal hydroxides can prepare with one of following several method: the preparation of available metal salt coprecipitation method, or metallic salt mixture thermolysis preparation, or with pickling process metallic salt be carried on the carrier, then dry, go thermolysis again, make purpose metal oxide or metal hydroxides.
64, according to the preparation method of claim 2 or 47 described phenol derivmives blend biologies, it is characterized in that step 2) obtain a mixture after having reacted, adopt underpressure distillation, separate the bromobenzene or the bromobenzene substituent that haunt and reacted, phenol or phenol substituent, water, remaining is metal bromide and hopcalite.
65, according to the preparation method of claim 2 or 47 described phenol derivmives blend biologies, it is characterized in that step 2) mixture that generates also can adopt spray-drying process to separate; In this process, water is arranged in the steam, do not have organic reactant, the product phenols of complete reaction, they will be separated in separation column; Isolated water and organic reactant can be utilized again; Remaining at last mineral compound.
66, according to the preparation method of the described phenol derivmives blend biology of claim 56, it is characterized in that the bromide of some metal, can oxidation get back to metal oxide in air or in the oxygen, these metal oxides or bromide are called as actives; In reaction, perhaps also exist with metal hydroxides owing to reacting with water; These metals comprise Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, Dy, V, Cr, Yb, Tm, Mn, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, Gd; More than the oxide compound or the oxyhydroxide of these metals in reaction, play active specy.
67, according to the preparation method of the described phenol derivmives blend biology of claim 63, it is characterized in that in the preparation process of purpose metal oxide or metal hydroxides, can adopt diverse ways that presoma is carried out drying, comprise in oven dry, vacuum-drying and the high temperature air or in the oxygen or calcination decomposition etc. in other special gas; These treating processess comprise these claims scope, but are not limited to these claims declared range.
68,, it is characterized in that mineral compound is metal oxide and metal bromide according to the preparation method of the described phenol derivmives blend biology of claim 64; They are in oxidation reactor, and with oxygen in oxygen or the air, oxidation regeneration is metal oxide and is regenerated as Br
2
69,, it is characterized in that mineral compound is metal oxide and metal bromide according to the preparation method of the described phenol derivmives blend biology of claim 65; They are in oxidation reactor, and with oxygen in oxygen or the air, oxidation regeneration is metal oxide and is regenerated as Br
2
70, the preparation method of coproduction aniline according to claim 3 and phenol derivmives blend biology is characterized in that step 1) hydrogen bromide HBr reclaims bromine through oxidation.
71, the preparation method of coproduction aniline according to claim 3 and phenol derivmives blend biology is characterized in that the said catalyzed reaction of step 1) can be a heterogeneous catalytic reaction, also can be homogeneous catalytic reaction.
72, the preparation method of coproduction aniline according to claim 3 and phenol derivmives blend biology, the reaction that it is characterized in that the said benzene of step 1) or benzene derivative and bromine can be that the reaction of operate continuously also can be a still formula batch reactions.
73, the preparation method of coproduction aniline according to claim 3 and phenol derivmives blend biology, it is characterized in that the said reaction of step 1) can be benzene or benzene derivative and bromine charging simultaneously, also can be one earlier after one, or a reactant once adds, another reactant adds in batches or continuously.
74, the preparation method of coproduction aniline according to claim 3 and phenol derivmives blend biology, it is characterized in that the said reaction of step 1) can carry out between-40 ℃ to 550 ℃, service temperature is-20 ℃ to 450 ℃ preferably, and best service temperature is-20 ℃ to 300 ℃.
75, the preparation method of coproduction aniline according to claim 3 and phenol derivmives blend biology, it is characterized in that the said reaction pressure of step 1) is between 0.1 normal atmosphere to 300 normal atmosphere, pressure range is between 0.5 normal atmosphere to 200 normal atmosphere preferably, preferably between 0.8 normal atmosphere to 50 normal atmosphere.
76, the preparation method of coproduction aniline according to claim 3 and phenol derivmives blend biology, the substituent that it is characterized in that the said benzene of step 1) comprises chloro thing, fluoro thing, bromo-derivative, phenyl substituent, alkyl substituent, alkenyl substituted thing, alkynyl substituted thing, nitro substituent, sulfo group substituent, phenylol substituent, thiophenol base substituent, the anilino substituent of benzene.
77, the preparation method of coproduction aniline according to claim 3 and phenol derivmives blend biology, it is characterized in that step 2) in bromobenzene and derivative and with ammoniacal liquor or volatile salt or ammonium bicarbonate aqueous solution and metal oxide or/and the metal hydroxides reaction, be added with further also that carrier loaded metal oxide, oxyhydroxide and auxiliary agent react and the mixture that generates aniline or anils and phenol or phenol derivatives has generated the metal bromide that metal bromide and ammino close in the reaction.
78, the preparation method of coproduction aniline according to claim 3 and phenol derivmives blend biology is characterized in that the described catalyzer of step 1) is metal oxide, metal chloride, metal fluoride, metal iodide, metal sulfate, metal phosphate, metal heteropolyacid salt, BF
3, the metal except that iron powder, and the arbitrary proportion mixture of above-listed compound.
79, the preparation method of coproduction aniline according to claim 3 and phenol derivmives blend biology is characterized in that the said catalyzer of step 1) can be homogeneous catalyst or heterogeneous catalyst.
80,, it is characterized in that the described catalyzer of step 1) can be loaded catalyst or unsupported catalyst according to the preparation method of claim 78 or 79 described coproduction aniline and phenol derivmives blend biology.
81, the preparation method of 0 described coproduction aniline and phenol derivmives blend biology according to Claim 8 is characterized in that said loaded catalyst contains a kind of mutually active and carrier of being made up of one or more metallic compounds of mixture.
82, the preparation method of 1 described coproduction aniline and phenol derivmives blend biology according to Claim 8 is characterized in that said carrier is meant to have a kind of being selected from as SiO at least
2, B
2O
3, Al
2O
3, GeO
2, TiO
2, ZrO
2, Nb
2O
5, Ta
2O
5, activated carbon etc. metallic compound or nonmetal or nonmetallic compound.
83, the preparation method of 1 described coproduction aniline and phenol derivmives blend biology according to Claim 8, it is characterized in that said activity of such catalysts is Li mutually, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Gr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, the oxide compound of Gd, fluorochemical, muriate, bromide, iodide, phosphoric acid salt, vitriol, carbonate, silicate, borate, and their mixture or their mixture and Ru, Rh, Pd, Ir, Pt, Ag, the mixture of metals such as Au and metallic compound.
84, according to the preparation method of claim 3 or 76 described coproduction aniline and phenol derivmives blend biology, it is characterized in that step 2) reaction can be batch-wise still reaction or successive reaction, the order of addition(of ingredients) of reactant can change arbitrarily.
85, according to the preparation method of claim 3 or 76 described coproduction aniline and phenol derivmives blend biology, it is characterized in that step 2) the ammoniacal liquor of reactant, wherein the ratio of ammonia and water can be an arbitrary proportion, and high density ammoniacal liquor can be depressed preparation adding, and ratio can be from 1: 99 to 99: 1; It influences the ratio of amine and phenol in the product than regular meeting; In the actual production, the aniline that can be as required or the ratio of aniline substituent and phenol or phenol substituent are determined ammonia concn.
86, preparation method according to claim 3 or 76 described coproduction aniline and phenol derivmives blend biology, it is characterized in that said metal oxide, metal hydroxides is meant Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, the oxide compound of Gd is or/and oxyhydroxide, and their oxide compound, the mixture of oxyhydroxide.
87, according to the preparation method of claim 3 or 76 described coproduction aniline and phenol derivmives blend biology, it is characterized in that said auxiliary agent is meant vitriol, phosphoric acid salt, carbonate, fluorochemical, muriate, bromide, iodide, silicate, borate, silico-aluminate, phosphomolybdate, the phospho heteropoly tungstate of listed metal in the claim 86, their oxide compound, oxyhydroxide, and the mixture of these compounds.
88, according to the preparation method of claim 3 or 76 described coproduction aniline and phenol derivmives blend biology, it is characterized in that the carrier in said load metal oxide and the oxyhydroxide is TiO
2, ZrO
2, HfO
2, Nb
2O
5, Ta
2O
5, MoO
3, WO
3, CeO
2, SiO
2, SnO
2, GeO
2, Bi
2O
3, Al
2O
3, activated carbon and their mixture.
89, according to the preparation method of claim 3 or 76 described coproduction aniline and phenol derivmives blend biology, it is characterized in that the preparation of said load metal oxide and oxyhydroxide, metal oxide, oxyhydroxide preparation, and the preparation that contains metal oxide, the oxyhydroxide of auxiliary agent can adopt the method for describing in claim 63 and 67, but is not limited to claim 63,67 and the said method of these claims.
90, according to the preparation method of claim 3 or 76 described coproduction aniline and phenol derivmives blend biology, it is characterized in that step 2) temperature of reaction is from 50 ℃ to 450 ℃, better is 80 ℃ to 400 ℃, preferably 100 ℃ to 350 ℃.
91, according to the preparation method of claim 3 or 76 described coproduction aniline and phenol derivmives blend biology, it is characterized in that step 2) reaction pressure is from 0.1 normal atmosphere to 400 normal atmosphere, pressure range is 0.5 normal atmosphere to 350 normal atmosphere preferably, preferably 1 normal atmosphere to 300 normal atmosphere.
92, according to the preparation method of claim 3 or 76 described coproduction aniline and phenol derivmives blend biology, it is characterized in that step 2) reaction can be with pure bromobenzene, bromobenzene derivative, also can be with their solution.
93, according to the preparation method of claim 3 or 76 described coproduction aniline and phenol derivmives blend biology, it is characterized in that step 2) reaction in ammoniacal liquor also can change (NH into
4)
2CO
3Or NH
4HCO
3The aqueous solution.
94, according to the preparation method of claim 3 or 76 described coproduction aniline and phenol derivmives blend biology, it is characterized in that step 2) aniline (or anils) in the product, phenol (or phenol derivatives), the bromobenzene (bromobenzene derivative), ammonia, the water that have not reacted, also available underpressure distillation separates, remaining inorganic solid compounds.
95, according to the preparation method of claim 3 or 76 described coproduction aniline and phenol derivmives blend biology, it is characterized in that step 2) aniline (or anils) is arranged in the product, phenol (or phenol derivatives), the bromobenzene that has not reacted (bromobenzene derivative), ammonia, water, and metallic compound and carrier and auxiliary agent (inorganics); Product is organic product, the reactant that has not reacted and water in the gas phase through spray evaporation, and they can feed separation column and separate; Solid phase is a metal oxide, metal hydroxides, metal bromide and carrier and auxiliary agent.
96,, it is characterized in that inorganic solid compounds is regenerated as metal oxide and bromine with dioxygen oxidation in oxygen or the air in the oxidation regeneration reactor according to the preparation method of described coproduction aniline of claim 94 and phenol derivmives blend biology.
97,, it is characterized in that it is that metal oxide and bromine recycle in the flow process that the inorganic solid compounds of being left will be placed in the interior oxidation regeneration of regeneration reactor according to the preparation method of described coproduction aniline of claim 95 and phenol derivmives blend biology.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021478643A CN100341846C (en) | 2002-12-12 | 2002-12-12 | Preparation for aniline, phenol and derivative thereof |
| AU2003211663A AU2003211663A1 (en) | 2002-12-12 | 2003-02-17 | Method of preparing aniline, phenol and their derivatives |
| PCT/CN2003/000134 WO2004052833A1 (en) | 2002-12-12 | 2003-02-17 | Method of preparing aniline, phenol and their derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021478643A CN100341846C (en) | 2002-12-12 | 2002-12-12 | Preparation for aniline, phenol and derivative thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1424304A true CN1424304A (en) | 2003-06-18 |
| CN100341846C CN100341846C (en) | 2007-10-10 |
Family
ID=4751347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021478643A Expired - Fee Related CN100341846C (en) | 2002-12-12 | 2002-12-12 | Preparation for aniline, phenol and derivative thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN100341846C (en) |
| AU (1) | AU2003211663A1 (en) |
| WO (1) | WO2004052833A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010034256A1 (en) * | 2008-09-29 | 2010-04-01 | 微宏动力系统（湖州）有限公司 | A process for producing phenol |
| US7838702B2 (en) | 2006-02-24 | 2010-11-23 | Basf Se | Direct amination of hydrocarbons |
| CN104437459A (en) * | 2014-11-18 | 2015-03-25 | 南京理工大学 | Activated carbon supported bismuth oxide and preparation method and application thereof |
| CN105384603A (en) * | 2015-12-09 | 2016-03-09 | 陕西省石油化工研究设计院 | Synthesis method of poly-fluorinated phenol compound |
| CN108499614A (en) * | 2018-04-28 | 2018-09-07 | 丛茜 | A kind of method that modified nickel catalytic material prepares central nervous system pharmaceutical intermediate |
| CN109046327A (en) * | 2018-09-14 | 2018-12-21 | 宁波中傲环保科技有限公司 | A kind of adsorption catalyst |
| CN109516920A (en) * | 2018-11-20 | 2019-03-26 | 浙江工业大学 | A kind of synthetic method of amantadine |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2921656B1 (en) | 2007-09-28 | 2012-11-02 | Centre Nat Rech Scient | PROCESS FOR THE SYNTHESIS OF ARYLAMINES |
| CN112374994B (en) * | 2020-12-08 | 2022-07-01 | 衢州学院 | Preparation method of pentafluoroaniline |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55116602A (en) * | 1979-03-05 | 1980-09-08 | Ishihara Sangyo Kaisha Ltd | Bromine recovering method |
| IL100537A0 (en) * | 1991-12-27 | 1992-09-06 | Chemagis Ltd | A process for the preparation of n-alkyl-3,4-dialkyloxyanilines and derivatives thereof |
| ES2114237T3 (en) * | 1994-02-11 | 1998-05-16 | Clariant Gmbh | PROCEDURE FOR THE PREPARATION OF FLUOROANILINES. |
-
2002
- 2002-12-12 CN CNB021478643A patent/CN100341846C/en not_active Expired - Fee Related
-
2003
- 2003-02-17 AU AU2003211663A patent/AU2003211663A1/en not_active Abandoned
- 2003-02-17 WO PCT/CN2003/000134 patent/WO2004052833A1/en not_active Application Discontinuation
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7838702B2 (en) | 2006-02-24 | 2010-11-23 | Basf Se | Direct amination of hydrocarbons |
| WO2010034256A1 (en) * | 2008-09-29 | 2010-04-01 | 微宏动力系统（湖州）有限公司 | A process for producing phenol |
| CN101712593B (en) * | 2008-09-29 | 2013-06-19 | 微宏动力系统（湖州）有限公司 | Method for preparing phenol |
| CN104437459A (en) * | 2014-11-18 | 2015-03-25 | 南京理工大学 | Activated carbon supported bismuth oxide and preparation method and application thereof |
| CN105384603A (en) * | 2015-12-09 | 2016-03-09 | 陕西省石油化工研究设计院 | Synthesis method of poly-fluorinated phenol compound |
| CN108499614A (en) * | 2018-04-28 | 2018-09-07 | 丛茜 | A kind of method that modified nickel catalytic material prepares central nervous system pharmaceutical intermediate |
| CN108499614B (en) * | 2018-04-28 | 2021-06-04 | 西南医科大学附属医院 | Method for preparing drug intermediate for central nervous system from modified nickel catalytic material |
| CN109046327A (en) * | 2018-09-14 | 2018-12-21 | 宁波中傲环保科技有限公司 | A kind of adsorption catalyst |
| CN109516920A (en) * | 2018-11-20 | 2019-03-26 | 浙江工业大学 | A kind of synthetic method of amantadine |
| CN109516920B (en) * | 2018-11-20 | 2021-10-01 | 浙江工业大学 | Synthesis method of amantadine |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003211663A1 (en) | 2004-06-30 |
| WO2004052833A1 (en) | 2004-06-24 |
| CN100341846C (en) | 2007-10-10 |
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